RU544240C - Method of obtaining olefin hydrocarbon - Google Patents

Abstract

METHOD FOR PRODUCING OLEPHIN HYDROCARBONS by dimerization or codimerization of olefins in the presence of a catalyst comprising a polymer containing nickel atoms complexed to electron-donating polymer groups and a cocatalyst-organoaluminum compound, characterized in that they are used to increase the efficiency of the process a catalyst whose polymer is a solvent swellable grafted copolymer of a polymer selected from the group consisting of natural rubber, ethylene propylene diene new polymers, polymers of diene and its copolymers with other monomers and organosilicon polymers containing vinyl groups with 4-vinyl pyridine containing 0.5-40 wt.% fragments of poly-4-vinylpyridine.

Description

The invention relates to petrochemistry, and in particular to methods for the dimerization and codimerization of olefins.

Known methods for the dimerization and codimerization of rlefins in the presence of catalysts of homogeneous and heterogeneous types.

Homogeneous catalysts representing a system: the compound of a transition metal with low molecular weight ligands containing elements of groups V and VI of the periodic system (nitrogen, oxygen, phosphorus, and sulfur) and an organoaluminum compound have a number of features. The most significant of these is the difficulty of isolating the desired products in pure form, since special methods are required to separate the components that are in one phase.

the complexity of creating continuous processes, as a rule, all methods are periodic. In addition, homogeneous catalysts are relatively unstable over time and do not regenerate.

The use of heterogeneous catalysts allows the process of dimerization and codimerization of olefins to be carried out continuously, however, when working with heterogeneous catalysts, only a part of the active centers is used and the speed of the process substantially depends on the structure and specific surface of the catalyst. In addition, with stirring of the reaction mass, the catalyst is crushed, resulting in significant losses.

There is also known a method of producing olefin oligomers by dimerization and codimerization of olefins in the presence of a catalyst - a metallized organic polymer containing group VIII metal atoms, complexed to electron-donating polymer groups by means of which metal atoms are attached to the polymer base and cocatalyst - an organoaluminum compound.

The electron-donating groups by which the Group VIII metal atoms are attached to the polymer base can be atoms of the elements of the hydrocarbon group, especially nitrogen, or elements of the group VIB, preferably oxygen.

The most typical metallized polymer is a transition metal compound, e.g. nickel, complexed to poly-4-vinylpyridine.

All the characteristics of heterogeneous catalysts are inherent in this catalyst.

The aim of the invention is to increase the efficiency of the process. To achieve this goal, it is proposed to use a catalyst whose polymer base is a swellable B: solvent grafted copolymer of rubber with poly-4-vinylpyridine containing 0.5-40% poly-4-imnylpyridine units. The proposed method for olefin dimerization and codimerization is in that the process is conducted in the presence of a catalytic system based on a transition metal of group VIII, for example, nickel, which is a swelling, but insoluble in the reaction medium gel, permeable throughout the volume to LD to the starting olefin, and for the reaction products. A similar catalytic system is obtained by reacting an organic polymer containing complex bound atoms of the transition metal Vli of the group of the periodic system, e.g. nickel, with a co-catalyst-organoaluminum compound.

A component of the gel catalyst system containing complex bound transition metal atoms is prepared by reacting a low molecular weight transition metal compound, e.g., a halide. acetylacetonate, alkoxide, and so on, with an organic polymer in the medium of hydrocarbons or their chlorine derivatives. The transition metal atoms are bonded to the polymer via electron donor groups that are included in the carrier polymer (0.540% by weight) and are located in the main chain or side branches of the polymer. Such groups may include groups containing elements of groups V-VI of the periodic system, preferably nitrogen, phosphorus, oxygen, sulfur, as well as various unsaturated bonds. At the end of the reaction, the resulting gel catalysts are thoroughly washed with a solvent to remove possible traces of the transition metal compound not chemically bonded to the polymer carrier.

Polymers and copolymers capable of dissolving or swelling in solvents used to dimerize and co-olefin olefins are used as the main substance of the carrier polymer, to which grafting electron-donor groups, for example vinyl pyridine, which are capable of complex binding of transition metal atoms, are used. natural and synthetic rubbers, for example, siloxane rubber (CKTB), 1,2-polybutadiene, ternary copolymers of ethylene, propylene and non-conjugated diene (various brands of CEPT),

5 cis-polybutadiene rubber (SKD), polyisoprene rubber (SKI) and others.

Organoaluminum compounds such as dialkylaluminium halide, alkylaluminoaluminium halide, aluminum sesqui-halide and others are used as cocatalyst.

Dimerization and codimerization of olefins is carried out in. an environment of aliphatic, acyclic, aromatic hydrocarbons or

5 of their chlorine-containing derivatives at O100 ° C, preferably at 20-50 ° C and a pressure of 0-100 atm, preferably 0-10 atm, in batch reactors with a stirrer or continuously in flow

0 tubular reactors.

The resulting catalyst is used in the form of granules swelling in a solvent of 0.1-5.mm in size or in the form of films, which, unlike heterogeneous catalysts, are easily permeable throughout the volume for reactant molecules and the resulting reaction products.

Unlike solid catalysts, the gel-like catalyst does not crush, easily

0 is regenerated and can be used for a long time while retaining its original activity.

The catalyst is characterized by higher activity, selectivity and increased specificity compared to known catalyst systems. Olefin dimerization products practically do not contain trimers and higher oligomers. By dimerizing ethylene, a 45% butene-1 content in

mixtures of butenes. Propylene dimerization products consist mainly of methyl pentenes.

Example 1. A. Preparation of a carrier.

In a 75 ml spherical ampoule equipped with a branch and a tube with a thin glass partition, a weighed portion of 1 g of industrial synthetic rubber is introduced (SKEPT - a triple copolymer of ethylene, propylene and dicyclopentadiene, unsaturation 1.96 e mol%), 0.11 g 4- vinylpyridine (4-VP) and 40 ml of gentane. 20 hours after the rubber was dissolved, the solution was degassed and 0.04 g of azobisisobutyric acid dinitrile was added in 5 ml of benzene. The ampoule is sealed and placed in a thermostat at 70 ° C for 10 hours. Then a thin glass septum is broken in vacuo and 0.04 g of benzoyl peroxide in 5 ml of benzene are introduced into the ampoule. The ampoule is sealed and placed in a thermostat at 80 ° C for 10 hours. The product is filtered off, washed twice with small portions (10 ml each) of benzene and dried in vacuo.

The carrier swells in hydrocarbon and chlorohydrocarbon solvents. The nitrogen content of 1.07 and 4-BH 9 wt.%.

B. Preparation of the catalyst.

A 100 ml glass reactor equipped with a stirrer is charged with O, 1 g of the obtained support in the form of granules 2-3 mm in size, 0.01 t of nickel acetylacetonate and 40 ml of heptane are added. The mixture was stirred at room temperature for 20 hours, then washed several times (4-6) with small portions (10 ml each) of heptane to remove unreacted nickel acetylacetonate. The nickel content of the resulting catalyst is 1.2 weight. %

B. Dimerization of ethylene.

The catalyst obtained in Example 1 B is loaded into the reactor, 0.5 ml of a 0.5 M solution of diisobutylaluminium chloride (DIBAC) in heptane and 10 ml of absolute heptane are introduced under argon atmosphere. The mixture was stirred 0.5 at 40 ° C and ethylene was introduced under a pressure of 2 atm. The reaction is carried out at a constant pressure of 2 atm at 40 ° C. After 2 hours, ethylene supply was stopped, and the resulting zylene ethylene dimers were distilled off and collected in a receiver. Get 9.5 g of butenes of the following composition, wt.%: Butene-1 37, cis-butene-2.26 and trans-butene-2 37 ..

Example 2 Propylene Dimerization

In a 40 ml glass reactor equipped with a stirrer, 0.1 g of the catalyst prepared according to the procedure of Example 1 is charged and 0.5 ml of a 0.5 M DIBAC solution and 10 ml of absolute heptane are introduced in the presence of air, the mixture is stirred for 0, 5 h. Then, at a temperature of 40 ° C, propylene is introduced under

pressure of 2.5 atm. The reaction is carried out at a constant pressure of 2.5 atm at a temperature of 40 ° C. After 2 hours, the supply of propylene was stopped, and the resulting hexanes 5 were collected in a receiver. The reaction rate is 600 g / g Ni h (7.2 g / g GCS).

The catalyst is highly stable over time.

After 30 days, 0 propylene was reintroduced into the reactor and dimerization was carried out under the given conditions, i.e. temperature 40 ° С and pressure 2.5 atm. The reaction rate remains unchanged.

Under identical conditions (pressure, temperature, nickel concentration) when using a gel-like catalyst, the propylene dimerization rate is three times higher than in the presence of a heterogeneous polymer catalyst. 0 PRI me R 3. Sodimerization of ethylene and propylene.

0.1 g of the catalyst prepared according to the procedure of Example 1 is loaded into a glass reactor with a stirrer, 0.5 ml of 0.5 M 5 DIBAC solution and 10 ml of absolute heptane are introduced. The mixture was stirred for 0.5 hours. An equimolecular mixture of ethylene and propylene was then fed and the reaction was carried out at a constant pressure of 2.5 atm and a temperature of 40 ° C. After 0 1 h, the olefin supply was stopped, and a mixture of CA, Cs and Ce olefins was obtained in an amount of 4.5 g containing 30 wt.% C5 olefins.

Example 4

A. Preparation of a carrier.

5 In a 250 ml three-necked flask equipped with a stirrer, argon supply tube and reflux condenser, 5 g of SCEPT (unsaturation of 2.75 mol%) in 50 ml of cyclohexane are placed and dissolved with stirring. Purified argon is then fed and boiled for 2 hours, cooled to 50 ° C, 0.45 g of 4-vinylpyridine and 0.015 gdinitrile of azobisisobutyric acid in 2 ml of benzene are introduced and heated at 70 ° C for 8 hours. . 2 ml of benzene

5 solution containing 0.02 g of benzoyl peroxide, and heated at 70 ° C for another 12 hours. The resulting product contains 1.13 wt.% Nitrogen, 10 wt.% 4-VP,

B. Preparation of the catalyst

0 0.1 g of washed and dried support is placed in a 40 ml metal reactor equipped with a stirrer. The reactor is evacuated and 10 ml of a nickel oleate benzene solution (0.032 g of oleate) are introduced.

5 nickel), incubated for 20 hours, washed with benzene (5 times 10 ml) and dried; The nickel content of the resulting catalyst was 1.31% by weight.

B. Dimerization of ethylene.

2 ml of a 0.5 M solution of DIBAC and 10 ml of absolute heptane are introduced into a metal reactor containing the washed catalyst. Ethylene is fed at a pressure of 10 atm and a temperature of 20 ° C. As a result of the reaction, the temperature rises to 30 ° C, at which the reaction is further conducted. After 1 h, reaction products were collected in a receiver. Obtain 24 g of a mixture of butenes.

The catalyst is also highly stable over time. After 30 days, ethylene was reintroduced into the reactor and dimerization was carried out at a temperature and pressure of 6 atm. After 1 h, the supply of ethylene is stopped, 15 g of a mixture of butenes are obtained.

PRI me R 5.

A. Preparation of a carrier,

1 g of 1.2-polybutadiene is placed in a D1-shaped ampoule and treated as described in Example 1A. The resulting carrier swells in hydrocarbon and chlorohydrocarbon solvents. The nitrogen content in the polymer is 1.4 wt .-% 4-VP 15 wt.%. B, Preparation of the catalyst. 0.5 g of carrier in the form of granules 2-3 mm in size are loaded into a 50 ml flask equipped with a stirrer. 04 g of nickel acetylacetonate and 300 ml of heptane. The mixture is stirred for 20 hours at room temperature, then, using a Soxhlet apparatus, nickel is washed from the unreacted acetylacetonate and the polymer is dried. A product is obtained with a nickel content of 1.56% by weight.

B. Dimerization of ethylene.

The catalyst is loaded into the tubular reactor and, in the absence of air, 2 ml of a 0.5 M solution of DIBAC and 30 ml of absolute heptane are introduced, and then ethylene is passed (pressure 2 atm). Dimerization products are collected in a receiver. Get a mixture of butenes of the following composition, wt.%: Butene-1 45, trans-butene-2 39 and cis-butane-2 16.

Example 6. Propylene dimerization.

Under the conditions of Example 5B, propylene was passed at a pressure of 2.6 atm. Dimerization products are collected in a receiver. Get a mixture of hexes of the following composition, wt.%: 4-methylenepentene-1.8, cis-4-methylpentene-2 12, trans-4-methylpentene-2 55.

a mixture of 2-methylpentene-1 and cis- and trans-2-methylpentene-2 20 and the remaining hexenes 5.

Example. A. Receiving media. In a spherical ampoule, 1 g of siloxane rubber (CTBT) was placed and treated as described in Example 1A. The resulting carrier swells in hydrocarbon and chlorohydrocarbon solvents. The nitrogen content in the polymer is 1.55 wt.%, 4-VP 20 wt.%.

B. Preparation of the catalyst.

0.1 g of the obtained support in the form of granules 2-3 mm in size, 0.01 g of nickel acetylacetonate and 20 ml of heptane are loaded into a glass reactor equipped with a stirrer. The mixture was stirred for 20 hours at room temperature, then washed several times with small portions of heptane. The nickel content in the resulting product is 1.5 wt.%.

B. Dimerization of ethylene.

To a reactor containing a catalyst,

5 obtained by the method of Example 7B, 0.7 ml of a 0.5 M solution (DIBAC) in heptane and 15 ml of absolute heptane are introduced under argon atmosphere. The mixture was stirred for 0.5 h at 20 ° C and ethylene was fed. The reaction is carried out

0 at a constant pressure of 2 atm at a temperature of 20 ° С. After 2 hours, ethylene supply is stopped, and the resulting dimerization products are collected in a receiver. Get a mixture of butenes of the following composition,

5 weight %: butene-1 36, cis-butene-2 22 and trans-butene-2 42.

PRI me R 8.

A. Preparation of a carrier.

In a spherical ampoule load 1 g of 0 natural rubber and process as described in example 1A. The resulting carrier swells in hydrocarbon and chlorohydrocarbon solvents. The nitrogen content in the polymer is 1.36 wt.%, 4-VP 13 wt.%. 5 B. Preparation of the catalyst.

In a glass reactor equipped with a stirrer, 0.1 g of the obtained support are loaded in the form of granules 2-3 mm in size and. treated as described in example 75, 0 A polymer with a nickel content of 1.55 wt.% is obtained.

B. Dimerization of ethylene.

In the absence of air, 0.7 ml of a 0.5 M solution of DIBAC in heptane and 15 ml of absolute heptane are introduced into the reactor containing the catalyst obtained according to the procedure of Example 8B, and the mixture is stirred for 0.5 h. Ethylene is then fed at 40 ° C. . The reaction is carried out at a constant pressure in

0 system 2 atm and temperature 4b ° С. After 2 hours, ethylene supply was stopped, and dimerization products were collected in a receiver. 8.7 g of a mixture of butenes are obtained.

Example 9 Propylene Dimerization

5 Under the conditions of Example 8, propylene is dimerized while maintaining a system pressure of 2.5 atm. Dimerization products are collected in a receiver. A mixture of hexenes is obtained, consisting mainly of 4-methyl and 2 methyl pentenes.

Example 10 Ethylene Dimerization

0.2 g of the support obtained by the procedure of Example 1 A containing 5 wt.% Poly-4-vinylpyridine units (nitrogen content in the polymer 0.65%), 0.01 g nickel acetylacetonate are loaded into a glass reactor equipped with a stirrer. and 40 ml of heptane. The mixture is stirred for several hours at room temperature, then washed several times with small portions (10 ml each) of heptane. The polymer was dried in vacuo, after which 0.5 ml and a 0.5 M solution of DIBAC in heptane and 15 ml of absolute heptane were introduced into the reactor. The mixture was stirred for 30 minutes at 40 ° C and ethylene was added. The reaction is carried out at a constant pressure of 2 atm and a temperature of 40 ° C. After 2 hours, ethylene supply was stopped, and the resulting reaction products were distilled off and collected in a receiver. Obtain 11.2 g of butenes of the following composition. weight.%; butene-1 39. cis-butene-2 25 and trans-butene-2 36..

Example 11. Ethylene Dimerization. In a 50 ml glass reactor equipped with a stirrer, 0.2 g of the support prepared according to the method of freezes 5A containing 40 wt.% Poly-4 vinylpyridine units (nitrogen content in the polymer 4.2%), 0.07 g of nickel acetylacetonate are loaded and 20 ml of heptane, the mixture is stirred for several hours at room temperature, then washed several times with small portions of heptane and the polymer is dried. 4 ml of a 0.5 M solution of ethyl aluminum dichloride in heptane and 15 ml of absolute heptane and then ethylene are introduced into the reactor. The reaction is carried out with stirring, a constant pressure of 3 atm and a temperature of 72 ° C. After 2 hours, the dimerization products are collected in a receiver. Get a mixture of butenes of the following composition, wt.%: Butene-1 35,

cis-butene-2 22, trans-butene-2 43.